Disazo dyes



United States Patent 3,369,013 DISAZO DYES Max A. Weaver, John I. Dale III, and James M. Straley,

Kingsport, Tenn., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed July 12, 1965, Ser. No. 471,456 8 Claims. (Cl. 260-186) This invention relates to new water insoluble disazo compounds useful as dyes for textile fibers, yarns and fabrics. In particular, the invention is directed to dyestuffs wherein the disazo component is preferably free of the vinylsulfonyl group.

The disazo compounds of the invention have the following general formula wherein R represents an azobenzene group preferably free of the vinylsulfonyl group, wherein the aromatic groups of the azobenzene radical include phenyl and substituted phenyl such as alkylphenyl, e.g. o,'n1,p-tolyl; alkoxyphenyl, e.g. o,m,p-methoxyphenyl; halophenyl, e.g. o,m,p-chlorophenyl; nitrophenyl, e.g. o,m,pnitrophenyl; alkylsulfonylphenyl, e.g. o,m,p-methylsulfonylphenyl; alkylsulfonamidophenyl, e.g. o,m,p-methylsulfonamidophenyl; di(alkylsulfonyDphenyl, e.g. 2,5-di(methylsulfonyl)phenyl; dicar'boxylicacidimidophenyl, e.g. 0,-m-succinimidophenyl; fluoroalkylphenyl, e.g. trifluoromethylphenyl; acylamidophenyl; e.g. o,m,p-acetamidophenyl; cyanophenyl, e.g. o,m,p-thiocyanophenyl; ralkylthiophenyl, e.g. o,m,pcarboxamidophenyl; benzamidophenyl; thiocyanophenyl, e.g. o,m,p-thiocyanophenyl;; alkylthiophenyl, e.g. o,m,pmethylthiophenyl; benzoxyphenyl, e.g. o,m,p-benzoxyphenyl; benzaminophenyl, e.g. o,m,p-benzaminophenyl; benzylaminophenyl, e.g. o,m,p-benzylaminophenyl; N-alkylbenzaminophenyl, e.g. N-phenylmethylaminophenyl; formylphenyl, e.g. o,m,p-formylphenyl; carbalkoxyphenyl, e.g. o,m,p-carbethoxyphenyl; benzoylphenyl, e.g. o,m,p benzoylphenyl;

R represents a monocyclic carbocyclic aromatic group of the benzene series including phenylene and substituted phenylene such as phenylene; alkylphenylene, e.g. o,m,- tolylene; alkoxyphenylene, e.g. o,m-methoxyphenylene, halophenylene, e.g. o,m-chlorophenylene; alkylsulfonylphenylene, e.g. o,m-methylsulfonylphenylene; alkylsulfonamidophenylene, e.g. o,m-methylsulfonamidophenylene; di(alkylsulfonyl)phenylene, e.g. 2,5-di(methylsulfonyl)- phenylene; dicarboxylicacidimidophenylene, e.g. o,m-succinimidophenylene; acylamidophenylene, e.g. o,m-acetamidophenylene; benzamidophenylene; thiocyanophenylene, e.g. o,m-thiocyanophenylene; alkylthiophenylene, e.g. o,m-methylthiophenylene; benzoxyphenylene, e.g. o,mbenzoxyphenylene; benzaminophenylene, e.g. o,m-benzaminophenylene; benzylaminophenylene, e.g. o,m-benzylaminophenylene; N-alkylbenzarninophenylene, e.g. o,m- N-phenylmethylaminophenylene; carbalkoxyphenylene, e.g. o,m-carbethoxyphenylene; benzoylp'henylene, e.g. o,m-benzoylphenylene;

R represents hydrogen or an alkyl radical including unsubstituted alkyl, preferably lower alkyl, i.e. from 1 to 4 carbon atoms, and substituted alkyl such as hydroxyalkyl, e.g. hydroxyethyl; polyhydroxyalkyl, e.g. glyceryl [CH(OH)CH(OH)CH OH]; alkoxyalkyl, e.g. methoxyethyl; cyanoalkyl, e.g. cyanoethyl; cyanoalkoxyalkyl, e.g. fi-cyanoethoxyethyl; acyloxyalkyl, e.g. acetoxyethyl, carbalkoxyalkyl, e.g. carbethoxyethyl; halogenoalkyl, e.g. chloroethyl; hydroxyhalogenoalkyl, e.g. fi-hydroxy-ychloropropyl; alksulfonylalkyl, e.g. methylsulfonylethyl;

3,369,013 Patented Feb. 13, 1968 alkyl-OCOOCH CH e.g. CH OCOOCH CH carboxamidoalkyl, e.g. carboxamidoethyl, benzyl, phenoxyalkyl, e.g. B-phenoxyethyl; cyanoalkyl, e.g. fi-cyanoethyl; alkylsulfonamidoalky, e.g. methylsulfonamidoethyl; alkylcarbonamidoalkyl, e.g. ethylcarbonamidoethyl; dicarboxamidoalkyl, e.g. fl-dicarboxamidoethyl, etc. or R represents a monocyclic carbocyclic aromatic radical of the benzene series, e.g. unsubstituted phenyl and substituted phenyl such as represented by R and R above, e.g. alkylphenyl, alkoxyphenyl, etc. As can be seen from the examples given below, the substituents attached to the R, R and R groups serve primarily as auxochrome groups to con trol the color of the disazo compound.

The Heyna et al U.S. Patent 2,784,204 granted Mar. 5, 1957 discloses monoazo compounds containing the vinylsulfone group, however such group, in all instances, is attached to the azo component of the dyestuff. Similarly, the Heyna et a1. U.S. Patent 2,657,205 granted Oct. 27, 1953 claims azo compounds containing the vinylsulfone group, however such group is, in all instances, attached to the azo component of the dyestutf and, additionally, the azo component must contain a sulfonic acid group. As described above, the present disazo compounds contain a vinylsulfonylethyl group which is attached to the coupling component and the disazo component is preferably free of such group. This distinctive structure imparts unexpected properties to the present disazo compounds, especially when the disazo compounds are used for dyeing textiles, including improved fastness to light and improved afiinity for polyester fibers. Thus, the disazo compounds in general can be expected to be superior to similar dyes containing the vinylsulfonyl or vinylsulfonylethyl group when tested by methods such as described in the A.A.T.C.C. Technical Manual, 1964 edition, depending in part upon the particular dye used and the fiber being dyed.

The disazo compounds of the invention are prepared by coupling well-known diazonium salts with the vinylsulfonylethyl-containing coupling components of the invention having the formula G H SOaCH=CH| wherein R and R have the meaning given above.

The coupling components having the Formula II are prepared by the following method:

+ CH2=CHSO2CH=CH3 The disazo compounds can be used for dyeing textile materials including synthetic polymer fibers, yarns and fabrics giving a variety of fast shades including red, orange, yellow and violet when applied there-to by conventional dye methods. The disazo compounds have mod erate to good alfinity for cellulose ester and polyamide fibers. When the disazo compounds are used for dyeing such hydrophobic materials, they should be free of watersolublizing groups such as sulfo and carboxyl. In general, the dyes have good fastness, for example, to light, washing, gas (atmospheric fumes) and sublimation.

The following examples will serve to illustrate the preparation of representative intermediates and disazo compounds of our invention.

3 EXAMPLES OF VINYLSULFONYLETHYL- ANILINE COUPLERS Preparation: of N-ethyl-N-fl-vinylsulfonylethylaniline 23.6 g. divinylsulfone, 24.2 g. N-ethylaniline and 105 ml. toluene were refluxed for 24 hours. The toluene was removed under reduced pressure and the product distilled at 167-183" C./O.75 mm. had the structure:

Preparation of N-ethyl-N-;8-vinylsulfonylethylm-toluidine 27 g. of N-ethyl-m-toluidine, 23.6 g. divinylsulfone, ml. acetic acid and "100 ml. toluene were mixed together and refluxed with stirring for 12 hours. The solvent was removed under reduced pressure and the product distilled under vacuum at 157159 C./ 0.35 mm. The product has the structure:

CitH4SO2CH=CH7 Q N i CH3 Preparation of N-ethyl-N-vinylsulfonylethylm-chlarotmilzne In accordance with the method of preparation previously set forth, a solution of divinylsulfone, 'N-ethyl-1nchloroaniline and toluene was refluxed to prepare the product which has the structure:

Preparation. of N-fl-hydroxyethyl-N-p-vinylsulfonylethyl-m-anisidine In accordance with the method of preparation previously set forth, a solution of divinylsulfone, N-B-hydroxyethyl-m-anisidine and toluene was refluxed to prepare the product which had the structure:

l C2H4OH O CH:

EXAMPLES OF THE DYES Example 1 To a solution of 1.44 g. sodium nitrite in ml. conc. sulfuric acid was added 20 ml. acid (1 part propionic acid: 5 parts acetic acid). 3.94 g. p-phenylazoaniline was added to the solution followed by 20 ml. of 1:5 acid. This solution was stirred for two hours and then added to a solution of 5.06 g. N-ethyl-N-fl-vinylsulfonylethyl-m-toluidine in 200 ml. 1:5 acid. The coupling solution was neutral-ized to brown on Congo Red paper with ammonium acetate and allowed to couple for two hours and was then washed, filtered and dried. The product dyes nylon, cellulose acetate, and polyester fibers bright orange shades of excellent fastness. The dye has the structure:

Example 2 1:5 acid. The solution was stirred for two hours and then added to a solution of 2.39 g. N-ethyl-N-;3vinylsulfonylethylaniline in 75 ml. 1:5 acid. The coupling solution was neutralized to brown on Congo Red paper with ammonium acetate and allowed to couple for two hours and was then washed, filtered and dried. The product dyes nylon, cellulose acetate and polyester fibers bright shades of orange. The product has the structure:

Example 3 The diazonium solution of Example 1 was added to a solution of 5.46 g. N-ethyl-N-vinylsulfonylethyl-m-chloroaniline in 150 ml. 1:5 acid. The coupling solution was neutralized to brown on Congo Red paper with ammonium acetate and allowed to couple for two hours. The coupling solution was then washed, filtered and dried. The product obtained dyes nylon, cellulose acetate and polyester fibers deep shades of orange. The dye has the struc ture:

Example 4 3.14 g. 3 acetamido 4-amino-2,5-dimethoxyazobenzone were diazotized using the same procedure and quantities of sodium nitrite, cone. sulfuric acid and 1:5 acid as in Example 2. The diazonium solution was added to a solution of 2.53 g. N-ethyl-N-fl-vinylsulfonylethyl-m-toluidine in ml. 1:5 acid. The solution was neutralized to brown on Congo Red paper with ammonium acetate and allowed to couple for two hours. The coupling solution was then washed, filtered and dried. The product obtained dyes nylon and polyester fibers deep shades of red. The dye has the structure:

I I CHsCNH O C H:

/ l /C:H4S0:CH=CH1 l l 02H: 0 C H3 0 Ha Example 5 4.62 g. 4-amino-3-chloroazobenzene were diazotized using the same procedure and quantities of reagents as described in Example 1. The resulting diazonium solution was added to a solution of 5.06 g. N-ethyl-N-fi vinylsulfonylethyl-m-tol-uidine in 200 ml. 1:5 acid. The solution was neutralized to brown on Congo Red paper with ammonium acetate and allowed to couple for two hours. The coupling solution was then washed, filtered and dried. The product dyes nylon a bright red shade with good fastness properties. The product has the structure:

C 2H5 0 H3 Example 6 2.25 g. 4-amino-2,3-dimethylazobenzene were diazotized using the procedure described in Example 2 and the resulting solution was added to a solution of 2.86 g. N-fl-hydroxyethyl-N-B-vinylsulfonylethyl-rn-anisidine in 50 ml. 1:5 acid. The solution was neutralized to brown on Congo Red paper with ammonium acetate and allowed to couple for two hours. The coupling solution was washed,

filtered and dried. The product dyes cellulose acetate and nylon red shades. The dye has the structure:

l C 2H4 O H C H:

CH: 0 CH3 The disazo compounds of the following table are made have varying utility as dyes. The degree of utility varies, for example, depending upon the material being dyed and the formula of the disazo compound. Thus, for example, all the dyes will not have the same degree of utility for the same material. As mentioned above, the substituents on the R, R and R radicals serve primarily as auxochrome groups to control the color of the disazo compound.

Polymeric linear polyester materials of the terephthalate type are illustrative of the linear aromatic polyester textile materials that can be dyed with the new diazo compounds of our invention. The terephthalate fibers sold under the trademarks Kodel, Dacron, and Terylene," for example, in the form of filaments, yarn and fabric, for example, are illustrative of the polyester textile mate- R1 rials that can be dyed. Kodel polyester fibers are more wherein A and B are optionally substituted as described particularly described in U.S. Patent 2,901,446. Dacron in the table. and Terylene polyester fibers are described, for example,

Azobenzene Component Vinylsulfonylethylaniline Coupler Example No. substituents on Substituents on Color Ring A ing Radical R1 Radical R; Nylon Dyeing Z-CH; 2-OH m-tolylene C:Ha Orange S-acetamido 2,5-di-OOH m-tolylene O=H Red. 3-hydroxymethyl 2,5-di-O CH m-tolylene --C2H5 Violet. 4-CH; 2 S-di-OOH: m-tolylene CH Do. 4-OH; 2,5-di-OH phenylene -C H4OH Orange None 2-chloro m-tolylene O;H Red. -OHS None rn-tolylene C'H CN Orange. 4-NHC O CH; None m-tolylene C2H4ON Do. 4-N O1 2,5-d1-0 CH m-tolylene O,H4ON Violet. 4N-(C H4OH); None m-tolylene -02H4ON Red. 4-OOCH; 3-CH3 m-Cl-phenylene O H5 Red. 4-01 Z-OH; phenylene CH3 Yellow. 4-OGH; 2,5-di-CH m-tolylene C:H4Cl Red. 4-013 2,5-di-OH m-OOH; phenylene H Reddishorange None None m-tolylene C:H4OOOCH Orange. None None m-tolylene --C:H4OCH Do. None None m-tolylene G H S O2OH3 Do.

C 0-CH1 24 None None m-tolylene G H N Do.

C OOHr 25 None None m-tolylene -o,H.oooNH Do.

6 None None o-tolylene hydrogen Yellow.

The disazo compounds of the invention may be used for dyeing hydrophobic fibers such as linear polyester, cellulose ester, acrylic, polyamide, etc., fibers in the manner described in U.S. Patents 2,880,050, 2,757,064, 2,782,187 and 2,043,827. The following examples illustrate methods by which the disazo compounds of the invention can be used to dye polyester textile materials.

0.1 g. of the dye is dissolved in the dye pot by warming in 5 cc. of ethylene glycol monomethyl ether. A 2% sodium-N-methyl-N-oleyl taurate and 0.5% sodium lignin sulfonate aqueous solution is added, with stirring, until a fine emulsion is obtained. Water is then slowly added to a total volume of 200 cc. 3 cc. ofDacronyx (a chlorinated benzene emulsion) are added and 10 grams of a textile fabric made of Kodel polyester fibers are entered. The fabric is worked 10 minutes without heat and then for 10 minutes at 80 C. The dye bath is then brought to the boil and held at the boil for one hour. Following this, the fabric is rinsed in warm water, then scoured in aqueous 0.2% soap, 0.2% soda ash solution. After scouring, the fabric is rinsed with water and dried. Accordingly, since the disazo compounds of the invention are Waterinsoluble, they can be applied from aqueous dispersions in the manner of the so-called dispersed dyes. However, coloration can be effected, for example, by incorporating the disazo compounds into the spinning dope and spinning the fiber as usual. The disazo compounds of our invention in U.S. Patent 2,465,319. The polymeric linear polyester materials disclosed in U.S. Patents 2,945,010, 2,957,745 and 2,989,363 for example, can be dyed. The linear aromatic polyester materials specifically named have a melting point of at least 200 C.

Nylon, in fiber, yarn and fabric form, is representative of polyamides which can be dyed with the disazo compounds.

The invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove, and as defined in the appended claims.

What we claim is:

1. A disazo compound of the general formula R1 RN=N--R1-NC 31148 0 7 C H: C H:

wherein R=an azobenzene radical free of a vinylsulfonyl group,

3,369,013 7 8 3. The compound 7. The compound C2H4SO2OH=CH2 H CHSCNH OCH:

4. The compound i C H 01 2:53 a

8. The compound 5. The compound (3H OCH;

01H References Citefi The compound FOREIGN PATENTS 779,781 7/1957 Great Britain.

(3211430 20 H=CH2 20 0 1H Ha D. M. PAPUGA, Assistant Examiner.

CHARLES B. PARKER, Primary Examiner. 

1. A DISAZO COMPOUND OF THE GENERAL FORMULA 